Surface-active agents



Patented Feb. 13, 1945 N. Y., assign'ors to" Eastman Kodak Company, Rochester, N. .,ya' corporation of New Jersey I No Drawing. Application December x A SerialNo. 512,966

n y 1 Claim. (01.260 61) This invention relates to the preparation and.

use of new organic compounds useful as surfaceactive agents and for related purposes and more particularly to sulfato derivatives of phosphonic acids having high chemical ness to hard water.

This application is a. continuation-impart of our copending allowed application, Ber. No.

"107,066, flied August 15, 1941.

The principal object of the invention is the production of a new class of organic chemical compounds which are useful as. surface-active agents such as wetting agents, dispersing or stability and inertemulsifying agents, penetrating agents, deterents and the like. A further object is to provide compounds which are useful as textile lubricants and anti-statics. A still further object is to pro vide a new class of derivatives of phosphonic acid. Other objects ,will appear hereinafter.

where R, R R. and R are groups selected from hydrogen, aryl, naphthenyl and alkyl, may be prepared by reacting phosphonic acids, having the graphic formula 11* on R m m- -a' tub tn particularly those co'mposed of or'containing lower aliphatic. acid esters oi cellulose such as cellulose acetate, cellulose propionate, cellulose.

acetate propionate and cellulose acetate butyrate.

;Many of these compounds are solvents for pr, soluble in mineral oils and in naturally-occurring blown or unblown animal and vegetable oils such as neatsfoot, olive, castor, soybean, sperm, eg and teaseed oils.

In the. following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof.

PREPARATION or Imlnmmrls The intermediates, that is, the acids from which the sulfate derivatives are obtained, may

r be prepared by the procedure set iorthin Compt.

rend. I I, 847; I33, 219; III, 234, 509 and Ann. chem. phys. (8) 3, 347; Text Book of Organic Chemistry, vol. XI, part III, chapter 1, page 41,

by J. N. Friend.

with a sulfating agent such as sulfuric acid,

oleum, suliurtrioxide, sulfuryl chloride, chlorosulfonic acid, sodium chlorosulfonate, or the like.

The products of this invention give calcium and magnesium salts which are sufllciently soluble in water to enable one to use these compounds in hard water without the formation of the obll. nis-a -hydroxybutmehypov homus acid.

jectionable precipitates obtained with soap. Because of this property, many of the products of this invention are valuable for many household purposes, such as the cleansing of cloth, dishes,

and the like. The products of this invention can also be used to advantage for practically any purpose where a surface-active compound is needed, for example, as dispersing, wetting,

emulsifying agents, as textile assistants and dyedispersing agents. Such compounds are of outstanding value for the lubrication and anti-static treatment of textile yarns, threads and fibers,

Among the intermediates useful for preparation or the sulfato derivatives of our invention are the following compounds, the description and preparation of which are indicated in each instance.

7 1. EMIrydroxybensylhypopbosphorous on 0 s Q 2. BB-c-llYdl'OXYhODtlflBhYWPhdSDl-LOIOUI acid.

H CtHn-C- P-OH 3. Bls a-bydroxypentanehypophospborous acid.

H [(hPc--l-P-OH E 4. Bisv-hydroxybutanahypophosphorous acid.

Ibid., p. 31!

Ibid., p. m

Ibid.. p. 843

. n [GHr-CHOH-CIb-C-l P.OH

6. Bis-rhydroxyiso-propylhypophoaphoroul acid. 7

Ann. Chem. plays. (5) s,p. 347

Ibid D- 325.

8. a-Hydroxybenzyl-u-hydroxyiso-propylhypophosphinic acid.

Ibid., p. 419 H /CH: Q i

on 1) OH CH:

9. H drox h t l -h drox 150- ro 1h 0 has hinic acid.

y yepyy y p by ypp p lbiduptm OH /CH: C\H1:lP-C 0H OH CH] a-Hydroxyisoamyl-mhydroxybenzylhypophosphlnlc acid.

0H 0H. 1 t c,n. 1k 0 0H 11. -a-Hydroxybenzyl-fl-bydroxybutylhypophosphinic acid.

' Ibid., p. 424

I OH on;

1 P\C OH k 0H CIH 12. -H drox h t 1- -h drox -lso-but 1h hos hinic acid.

a y y epy y y C 1?t.re nd.,138,p.1708

on on, Co 1r( J-P-0 OH OH cm. 13. a-Hydroxyethyl-Haydroxymethylbenzylhypopgiagplgniggcigbs H /CH; CHr-(J-PC OH H 0 0H Ph fi-e-Hydroxyamyl-a-hydroxybenzylhypophosphinic acid. Hid 40 l OH H H-*0 ii t 0116a 15. u-Hydroxy-no-propyl-a-hydroxyethylphosphinic acid. Ibid i\ E on, on 0 OH OH SYNTHESIS or NEW Inranmanmras In addition to the above known compounds, we have prepared a number of additional acids of this general type. Thefollowing examples describe the preparation and general characteristics of a number of these compounds.

Example 1 r 66 g. (1.0 mole) of hypophosphorous acid and 5 moles of mixed xylylpalmitylstearyl ketones are heated under carbon dioxide for two weeks at 100-105". On cooling, a solid separates that is filtered, washed with dilute alcohol, and dried. The compound has the formula: 65

(CHI):

0H {J-GuHn CnHaa U=P-Un I It is soluble in petroleum ether, acetic acid, and

-alcohol, and insoluble in water.

bid., p. 417

Example 2-Bis-a-hydrorynaphthenylhypophosphinous acid 6 moles dinaphthenyl ketone and (1.0 mole) 66 g. hypophosphorous acid are heated at -105 for two weeks and worked up as above. The

product thus obtained is a colorless mass, in-

soluble in water, and having the general solubility properties given above. The compound has the formula:

Example 4-Bis-a-hydrozrymethylamylhypophosphorous acid 66 g. (1.0 mole) hypophosphorous acid are heated on a steam bath with 10 moles methylbutylketone for 10 days. The ketone is removed under reduced pressure, and the product is dissolved in alkali and reprecipitated several times. It is soluble in the common organic solvents.

Exampl 5a-Hydroxy-a-naphthenylethyl-a-hydrowymethylamylhypophosphorous acid 66 g. (1.0 mole) hypophosphorous acid and 1.0 mole methylbutylketone are warmedon a steam bath for 20 hours; then 5-moles of meth'ylnaph-.

thenylketone are added and heated at 95-105 for two weeks. The acid is extracted with alkali and precipitated by adding acid. It has the general solubility properties previously described and the formula:

CH3 ('II) C4H0 Hoo P-COH H CH:

Naphthenyl Example 6-m Hydroayhemadecyl a hydrodymethylpropylhypophosphorous acid One mole of hexadecylaldehyde is reacted with 66 g. (1.0 mole) hypophosphorous acid at 95 for above examples, it is seen that the preparation of the hypophosphorous acids presents no special difficulties. Compounds of these general types may be reacted with organic acid halides or anhydrides to give the monoacyl esters having th general formula:

These are sulfated to give PREPARATION or THE SULFATO DERIVATIVES The preparation of the sulfato derivatives of our invention by reacting acids of the type above described with a sulfating agent is given below:

Example 7MO7lO-a-S1Llfllt0 a hydroxybisheptanehypophosphorous acid One mol of bis-a-hydroxyheptanehypophosphorous acid is placed in a flask fitted with a stirrer, dropping funnel, and thermometer with 500 cc. carbon tetrachloride. Then 1.1 moles of freshly distilled chlorosulfonic acid are added dropwise with stirring at room temperature over a period of one hour. The reaction mixture is slowly warmed to 90 On a steam bath to complete the reaction. The carbon tetrachloride is distilled off, and the product is evaculated under reduced pressure to remove the last of the product. It is a heavy, water soluble oil. The compound has the formula:

( n! on H CaHn-C then, a disulfato compound:

1 SOJH 011 is obtained.

Example 8-Bis-a-sulfatomethylhexylhypophosphorous acid One mole of bis-u-hvdroxymethylamylhypophosphorous acid is reacted exactly as in Example 7 with 2.2 moles freshly distilled chlorosulfonic acid. It is worked up exactly as in Example 1 and is a colorless water soluble acid having. the formula:

on, [HOSOr- P an. 2(") or If in place of 2.2 moles chlorosulfonic acid 1.1

i If about 2.2 moles chlorosulfonic acid are used,

moles had been used, the mono-sulfate compound 1 would have been obtained asin Example '7.

Example 9Bis-a-suljatoheptanehypophosphorcus acid One mole of bis-a-hydroxybutanehypophosphorous acid is reacted at 0 with 2.2 moles of chlorosulfonic acid dropwise with stirring. The reaction is completed and worked up as in Example 7. It is a colorless water soluble compound having the formula:

Example 10Bi8-a-8ulfatO-i.9oPr m/171111 97108- ,phorous acid CHz SOiH 2 Example 11-a-Sulfatoheptyl-a-suljato-iso-propylhypophosphorous acid One mole of a-hydroxyheptyl-a-hydroxy-isopropylhypophosphorous acid is sulfated exactly as in Example 7. The water soluble product has the formula:

By using 1.1 moles chlorosulfonic acid, the water soluble monosulfato compound is obtained.

Example 12-11-Sulfatoethyl-a-hydroxymethylbenzulhypophosphorous acid CH; H II orrr-oP-oosou1 H soil! One mole of a-hydroxyethyl-a-hydroxymethylbenzylhypophosphorous acid is sulfated exactly as in Example 7. The product is water soluble. By using oleum in excess at room temperature and slowly warming to a sulfonic acid group is introduced into the aromatic ring. Ice is added, and the compound on on.

SOzNa Example 13 One mole ofthe compound uHu 2 O-P-UH.

in 1 liter of carbon tetrachloride reacted with. 2.2 moles chlorosulionic acid and worked up after reacting as in Example '1 by removing the carbon tetrachloride and washing with water. The product has the formula CH I a): OSOH l (E-CuHu C11Hu and is slightly soluble in water. By using 1.1 moleschlorosulfonic acid, the monosulfato compound is obtained. The benzene ring may be sulfonated as in Example 12.

Example 14-Bis-a-sulfatonaphthenylhypophosphorous acid 1 mole of bis-a-hydroxynaphthenylhypophosphorous acid and 2.2 moles chlorosulfonic acid are reacted and worked up as in Example 7. The water solubleproduct has the formula:

naphthenyl O S ;.H naphthenyl naphtbenyl O OH naphthenyl 1.1 moles chlorosulfonic acid.

Example 15Bis-a-sulfato-p-:cenglamylhypophosphorous acid One mole of bis-oz-sulfato-p-xenylamylhypophosphorous acid is sulfated with 2.2 moles chlorosulfonic acid and worked up as'previously described. The water soluble product has the formula:

0=POH I The monosulfato is prepared in the usual manner.

The aromatic ring can be sulfonated as in Exam- Dle 12.

Example 16a-Sulfato-a-naphthenylethz/Z-asulfatomethylamz/Z-hypophosphorous acid One mole of a-hydroxy-c-naphthenylethyl-uhydroxymethylamylhypophosphorous acid is sulfated exactly as in Example 7 and worked up as therein described. The colorles water solubl product has the formula:

o-s 03-h OH 04H, naphthenyl-(f-fi-C-O-S 03H on, 0 CH1 By using one mole of chlorosulfonic acid, the mono ester is obtained.

Example 17Bis-a-sulfato-naphthenyl (mixed) (diethyl) phenylhypophosphorous acid One mole of bis-a-hydroxynaphthenyl (mixed diethyl) phenylhypophosphorous acid is sulfated with 2.2 moles chlorosulfonic acid exactly as in Example '7 and worked up as therein described. The water soluble product that results hasthe formula:

'25 The monosulfato compound is obtained by using The monosultato compound is prepared in the usual manner.

Example 18-a-Sulfa|toam:ul-a-acetomvamylhypophosphoric acid One mole of bis-a-hydroxyamylhypophosphorous acid is warmed on a steam bath with 1.1 moles acetic ,anhydride for 10 hours. The acetic acid and anhydride are removed under reduced pressure. The resulting water soluble product has the formula:

0-som 000-0111 One mole of a-sulfato-sec-butyl-ahydroxy# sec-butyl-hypophosphorous acid and 1 mole palmityl chloride are digested on the steam bath until no more hydrogen chloride. escapes. The

product is washed with water and dried. It is a-sulfato-sec butyl m palmitoxysecbutylhypophosphorous acid and has the formula:

on; osoin om 02H; Any acid anhydride such as propionic, methoxy acetic, sulfoacetic, benozic, heptoic, oleic, borezoic, naphthenic, and the like, and any ofthe acid chlorides such as benzoyl, palmityl, naphthenyl, oleyl, bateryl, etc., may be used.

The compositions of our invention are espe cially useful astextile lubricants and anti-statics for the conditioning of textile yarns, threads and fibers, particularly those composed of or containing organic derivatives of cellulose such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate and cellulose acetate butyrate to render such materials amenable to various textile operations including knitting, weaving, spinning, carding, twisting and the like.

In addition to the above-mentioned uses, the

compounds of our invention are especially efiective as detergents for washing textiles, china ware, cooking utensils and the like. These compounds may also be employed in place of ordinary soaps for shampooing, shaving and similar applications as well as in tooth paste and other prepa rations of like character. Their value for these purposes is primarily due to their inertness to hard water and to their chemical stability.

Not only may these materials be employed alone,

but they may also be employed as an adjunct to other detergent and surface-active agents formany industrial and domestic uses.

What we claim is:

As new chemical compounds sulfato derivatives of a, a? hydroxy phosphonic acids having the structural formula:

R3 on R1 s i i t n on A on wherein R, R R and R are substituents selected from the group consisting of hydrogen, aryl, naphthenyl and alkyl.

JOSEPH B. DICKEY.

- ANTHONY LORIA. 

